EP0915997A1 - Procedes de preparation de colloides metalliques stabilises par des solvants et de clathrates metalliques fixes sur des substrats - Google Patents

Procedes de preparation de colloides metalliques stabilises par des solvants et de clathrates metalliques fixes sur des substrats

Info

Publication number
EP0915997A1
EP0915997A1 EP97938826A EP97938826A EP0915997A1 EP 0915997 A1 EP0915997 A1 EP 0915997A1 EP 97938826 A EP97938826 A EP 97938826A EP 97938826 A EP97938826 A EP 97938826A EP 0915997 A1 EP0915997 A1 EP 0915997A1
Authority
EP
European Patent Office
Prior art keywords
metal
stabilized
solvent
colloids
size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97938826A
Other languages
German (de)
English (en)
Other versions
EP0915997B1 (fr
Inventor
Manfred Theodor Reetz
Gunther Lohmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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Publication of EP0915997A1 publication Critical patent/EP0915997A1/fr
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Publication of EP0915997B1 publication Critical patent/EP0915997B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention relates to two surprisingly simple methods for the size-selective production of soluble metal colloids and of carrier-fixed metal clusters.
  • the invention also includes the production of bimetallic colloids and carrier-fixed bimetallic clusters.
  • Nanostructured metal colloids or clusters in particular in the size range from 1 to 10 nm, are known to be useful catalysts. It has also long been known that the reduction of transition metal salts leads to insoluble metal powders, unless the reduction is carried out in the presence of stabilizers which wrap around the intermediately formed nanometer-sized metal clusters and protect them from undesired agglomeration [G. Schmid, Clusters and Colloids, VCH, Weinheim, 1994; BC Gates, L. Guczi, H.
  • the stabilizers known to date include special ligands such as triarylphosphines, polymers such as poly (vinylpyrollidones), surfactants such as long-chain tetraalkylammonium salts and in some cases special solvents.
  • the reducing agents required for the reduction of the metal salts include z. B. hydrogen, hydrazine, formaldehyde and various borohydrides a [Lit .: so].
  • the first electrochemical processes for the preparation of tetraalkylammonium salt-stabilized metal colloids and their carrier fixation have recently been described [MT Reetz, W. Heibig, J. Am. Chem.
  • a metal sacrificial anode e.g. a Pd sheet
  • R 4 N + X " the metal sheet dissolves anodically, the metal salts which form thereby migrate to the cathode, where they are reduced again.
  • the metal atoms accumulate to form nanostructured metal colloids, which are stabilized by the tetraalkylammonium salts.
  • a major advantage of the method is the fact that the size of the nanostructured R- t , N + X ' -stabilisier.en cluster can be varied by adjusting the current density. This is important because, as is well known, the size of metal clusters strongly influences their catalytic properties [G. Schmid, Clusters and Colloids, VCH, Weinheim, 1994]. In fact, controlling cluster size is considered the greatest challenge in this area [JS Bradley, in Clusters and Colloids, (ed. G. Schmid), VCH, Weinheim, 1994, p. 490].
  • metal colloids can also be produced using metal evaporation [SC Davis, KJ Klabunde, Chem. Rev. 82 (1982) 153; KJ Klabunde, G. Cardenas-Trivino, in Active Metals: Preparation, Characterization, Applications (ed. A. Mariestner), VCH, Weinheim, 1996, p. 237].
  • a transition metal is then evaporated and the metal vapor is brought into a cold matrix consisting of a solvent.
  • the metal colloid solutions generated at low temperatures could be brought to room temperature without undesired agglomeration of the nanostructured metal clusters. It is solvent stabilization. Some of the solvent-stabilized metal colloids depicted in this way were used as catalysts in hydrogenations. This method avoids the disadvantages mentioned above. However, metal evaporation is an expensive method because complex equipment with high energy consumption is required. The size selectivity on a preparative scale is also problematic. Is used to reduce Pd salts hydrogen in special solvents such as propylene carbonate, such. B. in the in situ hydrogenation of fatty acids, solvent-stabilized Pd clusters are involved as hydrogenation catalysts [A.
  • Another method relates to the simple thermolysis of certain transition metal salts in methyl isobutyl ketone as a solvent and stabilizer.
  • this solvent stabilizes Pd clusters.
  • the Pd clusters are relatively large, i.e. H. greater than 8 nm, further control of the cluster size, i. H. size selectivity not possible [K. Esumi, T. Tano, K. Meguro, Langmuir 5 (1989) 268].
  • the metal colloids according to the invention do not require any surfactants or polymers for stabilization.
  • Me z oxidized metal as an intermediate salt
  • Me ko ⁇ / solvent solvent-stabilized metal colloid
  • transition metal salts as the metal source in the electrochemical production of solvent-stabilized metal colloids.
  • An electrochemical apparatus consisting of two inert electrodes is used. Both variants include the use of solvents that are capable of stabilizing metal colloids or metal clusters, as well as a suitable conductive salt.
  • transition metals such as Fe, Co, Ni, Pd, Cu, Ag or Au are used.
  • transition metal salts a wide variety of salts of transition metals, e.g. B. of Fe, Co, Ni, Pd, Pt, Rh, Ru, Mo, Cu, Ag or Au.
  • Polar solvents such as organic carbonates (e.g. propylene carbonate), carboxamides (e.g. dimethylacetamide), sulfuric acid amides (e.g. S ⁇ 2 (NBu 2 ) 2) or urea derivatives (e.g. Tetrabutylurea).
  • Propylene carbonate is preferably used.
  • NaCl or (C ⁇ N + X- is preferably used as the conductive salt.
  • the temperature in the electrolysis cell can be between -50 ° C and + 140 ° C, preferably 25-70 ° C.
  • transition metal salts are heated in a suitable solvent.
  • the salt is converted into the metallic form, the latter being in the form of soluble nanostructured metal colloids or metal clusters which are stabilized by the solvent.
  • polar solvents such as organic carbonates, carboxamides, sulfuric acid amides or urea derivatives, preferably propylene carbonate, are particularly suitable for stabilizing the colloids or clusters.
  • the preparation is carried out by heating the solution or suspension of a transition metal salt in the presence of an alcohol in the solvent, in the range from 30 ° to 130 ° C., preferably at 60 to 100 ° C.
  • Typical salts are PdCl 2 , Pd (OAc) 2 , Pd (acac) 2 , Ni (OAc) 2 , Fe (acac) 2 , Fe (OAc) 3 , PtCl 2 , Pt (OAc) 2 , RhCl 3 , Rh ( OAc) 3 , Co (OAc) 2 , Cu (OAc) 2 AgOAc or Ag 2 CO 3 .
  • the nature of the alcohol used for the reduction is decisive for the size selectivity. Branched alcohols such as B. isopropanol lead to small clusters, e.g. B. in the 2-5 nm range, while methanol provides larger clusters, typically in the range of 6 to 10 nm.
  • Two metal sources are required for the production of solvent-stabilized bimetallic coids or clusters.
  • electrochemical method There are three variants of the electrochemical method: 1) use of two sacrificial anodes; 2) use of sacrificial anode and metal salt; 3) Use of two different metal salts.
  • two different metal salts are dissolved or suspended in a suitable polar solvent in the presence of an alcohol and then heated.
  • TEM transmission electron microscopy
  • the size of the colloids or clusters produced according to the invention is in the nanometer range, typically between 2 and 15 nm. As far as the size distribution of the metal clusters is concerned, they are surprisingly uniform. As far as thermal stability is concerned, many of the colloidal solutions shown according to the invention are unusually stable. A 0.1 M propylene carbonate solution of 8-10 nm Pd clusters is typical, which is stable for at least 3 days at 160 ° C or shows no sign of Pd powder bonding. This is in contrast to conventionally stabilized metal clusters, such as. B. R4N + K '-stabilized Pd colloids that decompose rapidly at 130 - 140 ° C. This unusually high thermal stability of the solvent-stabilized KoUoide is an unexpected property, which is particularly useful when used in catalysis
  • the solvent-stabilized metal or bimetallic clusters described here can also be fixed to supports.
  • the colloidal solutions are treated with solid, optionally doped supports such as metal oxides (e.g. SiO 2 , Al 2 O 3 , or TiO 2 ), activated carbon or polymers (e.g. polyaramides).
  • metal oxides e.g. SiO 2 , Al 2 O 3 , or TiO 2
  • activated carbon or polymers e.g. polyaramides
  • the solid support is allowed to settle, filtered or decanted and the solid is dried. If pellets are used as carriers (e.g. Al 2 O 3 pellets), shell catalysts are easy to produce.
  • Both the koUoidal solutions and the support-fixed forms of the metal clusters are suitable as catalysts for a variety of different reactions, such as. B. hydrogenations, Oxidaüonen and CC linkages.
  • propylene carbonate-stabilized Pd clusters are suitable as catalysts in the Heck reaction of chloraro aten at 130-160 ° C.
  • Example 4 Representation of propylene carbonate-stabilized rhodium colloid
  • the thermal stability of propylene carbonate-stabilized palladium koUoids relative to that of J- ⁇ -TX " palladium koUoids can be determined as follows.
  • a palladium koUoid (size 8-10 nm) obtained according to the above examples is three days to 150-160 ° C. There is no precipitation of palladium powder or an optical change.
  • a solution containing 112 mg of chlorobenzene, 106 mg of sodium carbonate, 157 mg of styrene and 1 ml of propylene carbonate-stabilized 0.001 molar KoUoid solution is heated under argon in a closed vessel to 155 ° C. for 17 h. At the end of the reaction, 2 ml of diethyl ether are added and the mixture is filtered. The isolated yield of trans-stilbene is 15%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Colloid Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

On réduit cathodiquement par voie électrochimique des colloïdes de métaux de transition stabilisés par des solvants pour obtenir des colloïdes métalliques par l'intermédiaire de sels métalliques en présence de solvants stabilisants polaires, ou on réduit les sels des métaux de transition dans un solvant polaire au moyen d'un alcool à une température accrue.
EP97938826A 1996-07-30 1997-07-16 Procedes de preparation de colloides metalliques stabilises par des solvants et de clathrates metalliques fixes sur des substrats Expired - Lifetime EP0915997B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19630581 1996-07-30
DE19630581A DE19630581A1 (de) 1996-07-30 1996-07-30 Verfahren zur Herstellung von Solvens-stabilisierten Metallkolloiden und trägerfixierten Metallclustern
PCT/EP1997/003807 WO1998004763A1 (fr) 1996-07-30 1997-07-16 Procedes de preparation de colloides metalliques stabilises par des solvants et de clathrates metalliques fixes sur des substrats

Publications (2)

Publication Number Publication Date
EP0915997A1 true EP0915997A1 (fr) 1999-05-19
EP0915997B1 EP0915997B1 (fr) 2002-03-27

Family

ID=7801188

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97938826A Expired - Lifetime EP0915997B1 (fr) 1996-07-30 1997-07-16 Procedes de preparation de colloides metalliques stabilises par des solvants et de clathrates metalliques fixes sur des substrats

Country Status (7)

Country Link
US (1) US6224739B1 (fr)
EP (1) EP0915997B1 (fr)
JP (1) JP2000516995A (fr)
AT (1) ATE215135T1 (fr)
CA (1) CA2262105A1 (fr)
DE (2) DE19630581A1 (fr)
WO (1) WO1998004763A1 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6607829B1 (en) * 1997-11-13 2003-08-19 Massachusetts Institute Of Technology Tellurium-containing nanocrystalline materials
US6207392B1 (en) * 1997-11-25 2001-03-27 The Regents Of The University Of California Semiconductor nanocrystal probes for biological applications and process for making and using such probes
JP4871443B2 (ja) * 2000-10-13 2012-02-08 株式会社アルバック 金属超微粒子分散液の製造方法
US6576291B2 (en) 2000-12-08 2003-06-10 Massachusetts Institute Of Technology Preparation of nanocrystallites
DE10211701A1 (de) * 2002-03-16 2003-09-25 Studiengesellschaft Kohle Mbh Verfahren zur in situ Immobilisierung von wasserlöslichen nanodispergierten Metalloxid-Kolloiden
US7229497B2 (en) * 2003-08-26 2007-06-12 Massachusetts Institute Of Technology Method of preparing nanocrystals
CN100348564C (zh) * 2003-09-05 2007-11-14 帝斯曼知识产权资产管理有限公司 二苯乙烯衍生物的制备方法
DE102004002576A1 (de) * 2004-01-17 2005-08-04 Bayer Ag Verfahren zur Hydrierung von Doppelbindungen-enthaltenden, ungesättigten Polymeren
US7253452B2 (en) 2004-03-08 2007-08-07 Massachusetts Institute Of Technology Blue light emitting semiconductor nanocrystal materials
US7229690B2 (en) * 2004-07-26 2007-06-12 Massachusetts Institute Of Technology Microspheres including nanoparticles
US7316967B2 (en) * 2004-09-24 2008-01-08 Massachusetts Institute Of Technology Flow method and reactor for manufacturing noncrystals
US8134175B2 (en) 2005-01-11 2012-03-13 Massachusetts Institute Of Technology Nanocrystals including III-V semiconductors
ITPI20060011A1 (it) * 2006-01-26 2007-07-27 Univ Pisa Procedimento per la preparazione di catalizzatori metallici nanostrutturati e loro impiego in reazioni catalitiche
JP4849317B2 (ja) * 2006-03-24 2012-01-11 住友電気工業株式会社 金属微粒子の製造方法
KR100907877B1 (ko) * 2007-03-15 2009-07-14 윤의식 금속 나노입자 콜로이드 용액 제조 방법 및 이를 이용한 금속 나노입자 분말 제조 방법
JP5202858B2 (ja) * 2007-03-23 2013-06-05 古河電気工業株式会社 銅微粒子の製造方法
EP2123797B1 (fr) * 2008-04-29 2015-08-12 Universita' Degli Studi di Bari Nanomatériaux pour libération contrôlée de métal et leur procédé de fabrication
RU2408740C2 (ru) * 2008-06-20 2011-01-10 Государственное учебно-научное учреждение Химический факультет Московского государственного университета им. М.В. Ломоносова Электрохимический способ получения металлического вольфрама в высокодисперсном реакционноспособном состоянии
RU2410471C1 (ru) * 2009-09-01 2011-01-27 Общество с ограниченной ответственностью "Научно-производственное объединение "Ликом" Способ получения наночастиц металлов в водной среде
RU2410472C1 (ru) * 2009-09-01 2011-01-27 Общество с ограниченной ответственностью "Научно-производственное объединение "Ликом" Способ получения наночастиц меди в водной среде
US9938628B2 (en) * 2015-05-19 2018-04-10 General Electric Company Composite nanoparticles containing rare earth metal and methods of preparation thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532518A (en) * 1967-06-28 1970-10-06 Macdermid Inc Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions
US4877647A (en) * 1986-04-17 1989-10-31 Kansas State University Research Foundation Method of coating substrates with solvated clusters of metal particles
JPH01315334A (ja) * 1988-06-11 1989-12-20 Nisshinbo Ind Inc 金属コロイド分散液
US5147841A (en) * 1990-11-23 1992-09-15 The United States Of America As Represented By The United States Department Of Energy Method for the preparation of metal colloids in inverse micelles and product preferred by the method
DE4111719A1 (de) * 1991-04-10 1992-10-15 Studiengesellschaft Kohle Mbh Verfahren zur herstellung hochaktiver, dotierter metall-traegerkatalysatoren
DE69510477T2 (de) * 1994-03-14 2000-03-16 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von hoch verstreuten Metall-Kolloiden und von auf einem Substrat gebundenen Metall-Clusters durch elektrochemische Reduktion von Metallsalzen
DE4443392A1 (de) * 1994-12-06 1996-06-13 Studiengesellschaft Kohle Mbh Elektrochemische Reduktion von Metallsalzen als Verfahren zur Herstellung von hochdispersen Metallkolloiden und trägerfixierten Metallclustern
DE4408512A1 (de) * 1994-03-14 1995-09-21 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von hochdispersen Metallkolloiden und trägerfixierten Metallclustern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9804763A1 *

Also Published As

Publication number Publication date
US6224739B1 (en) 2001-05-01
CA2262105A1 (fr) 1998-02-05
DE19630581A1 (de) 1998-02-05
JP2000516995A (ja) 2000-12-19
WO1998004763A1 (fr) 1998-02-05
ATE215135T1 (de) 2002-04-15
EP0915997B1 (fr) 2002-03-27
DE59706780D1 (de) 2002-05-02

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